title: Hematin crystallization from aqueous and organic solvents.
abstract: Hematin crystallization is the main mechanism of detoxification of heme that is released in malaria-infected erythrocytes as a byproduct of the hemoglobin catabolism by the parasite. A controversy exists over whether hematin crystals grow from the aqueous medium of the parasite's digestive vacuole or in the lipid bodies present in the vacuole. To this end, we compare the basic thermodynamic and structural features of hematin crystallization in an aqueous buffer at pH 4.8, as in the digestive vacuole, and in water-saturated octanol that mimics the environment of the lipid nanospheres. We show that in aqueous solutions, hematin aggregation into mesoscopic disordered clusters is insignificant. We determine the solubility of the β-hematin crystals in the pH range 4.8-7.6. We image by atomic force microscopy crystals grown at pH 4.8 and show that their macroscopic and mesoscopic morphology features are incompatible with those reported for biological hemozoin. In contrast, crystals grown in the presence of octanol are very similar to those extracted from parasites. We determine the hematin solubility in water-saturated octanol at three temperatures. These solubilities are four orders of magnitude higher than that at pH 4.8, providing for faster crystallization from organic than from aqueous solvents. These observations further suggest that the lipid bodies play a role in mediating biological hemozoin crystal growth to ensure faster heme detoxification.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas 77204, USA.
authors.forename: Megan A
authors.initials: MA
authors.lastname: Ketchum
authors.forename: Katy N
authors.initials: KN
authors.lastname: Olafson
authors.forename: Elena V
authors.initials: EV
authors.lastname: Petrova
authors.forename: Jeffrey D
authors.initials: JD
authors.lastname: Rimer
authors.forename: Peter G
authors.initials: PG
authors.lastname: Vekilov
mesh_terms: D000818:Animals; D003460:Crystallization; D006420:Hemeproteins / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D018625:Microscopy, Atomic Force; D008855:Microscopy, Electron, Scanning; D000442:Octanols / Q000737:chemistry*; D010316:Particle Size; D012995:Solubility; D012997:Solvents / Q000737:chemistry; D013499:Surface Properties; D013552:Swine; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D006420:Hemeproteins; D000442:Octanols; D012997:Solvents; D014867:Water; C020753:hemozoin